Synthetic and Electron Spin Resonance Studies of Six-Coordinate Complexes Related by Electron-Transfer Reactions

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

“…Here, covalent contributions to the bonding result in a deviation of R g from unity (0:5 R g 1:0). Maki and co-workers (387,388,409,420) showed that the measured g values did not agree well with the theory, as unrealistically small, or negative, values of R g were required to explain the data. Further analysis of these complexes focused on the hyperfine coupling.…”

“…As for the metallo-mono(dithiolenes) and metallo-bis(dithiolenes), the EPR spectroscopy of metallo-tris(dithiolenes) has been particularly informative, if not controversial, in the determination of the singly occupied HOMO of these complexes. Among the earliest EPR studies in this area are those of Maki and co-workers (387,388,409,420). These researchers immediately realized that the highly covalent nature of the bonding in metallotris(dithiolenes) resulted in questioning the applicability of formal oxidation state assignments for the metal and dithiolene ligands.…”

“…McGarvey (421) also developed expressions for the anisotropic hyperfine interaction and the reduced form of these equations were used by Maki and co-workers (420) in their analysis of the hyperfine coupling in metallotris(dithiolenes). These equations are given below: 2À host, the ion adopts a D 3 structure with a trigonal twist angle of $28…”

Synthesis, characterization, magnetic, thermal and redox properties of oxovanadium(IV) complex of heterocyclic acid hydrazone

“…A band at 1590 cm -1 is due to new ν(C=N) (Figure 3). The complex exhibits a broad band at 3070 cm -1 and this is due to the presence of lattice water [15][16][17][18]. In the free ligand 2-thiophenecarbanicotinic hydrazone, thiophene ring shows absorption band at 846 cm -1 .…”

A computational investigation into nickel-bis(diselenolene) complexes as potential catalysts for reduction of H+ to H2

“…2, 15 The unique chemistry of dithiolene containing complexes is a result of the noninnocent interaction between metal and ligands. 16 Dithiolene ligands are in fact prototypical redox-noninnocent ligands and undergo reversible redox reactions when coupled to a metal. An advantage of such redox-active ligands is that by varying the R-groups attached to the ligand properties of the complex can be tuned for a specific application.…”